Smell-sweetening and deodorizing maleimides

ABSTRACT

A smell-sweetening and deodorizing agent comprising as an active ingredient a maleimide derivative expressed by the general formula:   WHEREIN R1 stands for hydrogen or an organic group, and R2 and R3 are selected from the group consisting of hydrogen, halogen and organic groups, provided that R2 and R3 do not comprise parts of the same ring.

United States Patent [191 Masuda et al.

[ SMELL-SWEETENING AND DEODORIZING MALEIMIDES [75] Inventors: Fumiya Masuda; Meiken Nakaiima,

both of lchikawa; Yukio Oyamada, Funabashi, all of Japan [73] Assignee: Kao Soap Co., Ltd., Tokyo, Japan [22] Filed: June 19, 1972 [21] Appl. No.: 264,266

[30] Foreign Application Priority Data June 21, 1971 Japan 46-44726 Dec. 28, 1971 Japan (46-2775 [52] US. Cl. 424/76, 424/274 [51] Int. Cl A611 13/00 [58] Field of Search 424/76, 274

[56] References Cited UNITED STATES PATENTS 2,726,981 12/1955 Wolf et a1. 424/274 3,317,372 5/1967 l-lart 424/76 3,459,852 8/1969 Roehm 424/76 3,632,514 1/1972 Blocker 424/76 3,650,968 3/1972 Hoffman 424/76 Oct. 22, 1974 OTHER PUBLICATllONS Chemical Abstracts, Vol. 75, 106574d.

Primary Examiner-Vincent D. Turner Attorney, Agent, or Firm-Woodhams, Blanchard and Flynn 57 ABSTRACT A smell-sweetening and deodorizing agent comprising as an active ingredient a maleimide derivative expressed by the general formula:

2 Claims, N0 Drawings eral formula (I) are listed in Table 1.

SMELL-SWEETENING AND DEODORIZING MALEIMIDES BACKGROUND OF THE INVENTION 1. Field Of The Invention This invention relates to a smell-sweetening and deodorizing agent which is effective for removing bad smells, especially those of mercaptans and hydrogen sulfide, in lavatories, dust bins, livestock pens, etc.

2. Description Of The Prior Art For the deodorization of lavatories or dust bins, methods for masking odors with perfumes or the like have heretofore been mainly adopted.

Deodorizing agents capable of chemically removing bad smells, for instance, agents containing citric acid or maleic acid, as a main ingredient, have been known. These deodorizing agents are relatively effective for ammonia and amines, but they are incapable of removing the smellsof mercaptans and hydrogen sulfide.

SUMMARY OF THE INVENTION We have carried out extensive research with a view to providing a compound capable of removing bad smelling components such as mercaptans and hydrogen sulfide. We have discovered that a series of maleimide derivatives expressed by the following general formula wherein R stands for hydrogen or an organic group,

and R and R are selected from the group consisting of hydrogen, halogen and organic groups,

are effective for the above purpose. Based on this discovery, we have achieved this invention.

Examples of organic groups represented by R,, R and R in above general formula (I) are alkyl groups I having l-l2 carbon atoms such as methyl, ethyl, n-

. nyl wherein the alkyl has 1 to 3 carbon atoms, anilino and phenylhydrazo.

Examples of maleimides expressed by the above gen- TABLE l-Continucd In Above (icncrul Formula (I) In this invention, the substituents R R and R in general, are not critical, except that R and R cannot form parts of the same ring.

It has been found that the various compounds having structures similar to, but different from, that of the maleimide derivative of above general formula (I), such as N-ethyl succimide, phthalimide, N- hydroxyethyl phthalimide, N-methyl pyrrolidone, cyanuric acid, maleic acid, esters and. amides thereof, fumaric acid, N-methyl butyrolactarn and dimethyl succimide do not exhibit any substantial deodorizing effect for mercaptans and hydrogen sulfide. Based on this finding it has been confirmed that in order to remove mercaptans and hydrogen sulfide from a complicated putrefaction system, the presence of the characteristic maleimide grouping is essential. Further, it has been confirmed that a deodorizing effect cannot be obtained by compounds of general formula I in which R and R together form a single ring, namely compounds expressed by the following general formula (II):

wherein R, and R are as listed below:

RI n

CHzOH 2); 3 -2J4 CH CH 2): uHs zla The active ingredient of the smell-sweetening and deodorizing agent of this invention expressed by general formula I reacts with mercaptans and hydrogen sulfide and removes the bad smell thereof quite rapidly.

The use of a compound expressed by general formula I alone does not exhibit a sufficient effect for removing the odor of ammonia and amines, but when it is used in combination with known deodorizing agents for ammonia and amines, such as acids, e.g., citric acid, malic acid, oxalic acid, glycolic acid phosphoric acid, tartaric acid and maleic acid andaldehydes, e.g.. glyoxal and glutaraldehyde, there can be provided a chemical deof N-ethyl maleimide, 2% of glyoxal and 0.4% of benzalkonium chloride. The excellent results as shown in Table 3 were obtained.

3 4 odorizing composition which exhibits deodorizing ef- Table 3 fects in a broad range of applications. An effective chemical deodorizing composition comprises from 0.1 Momma" Hydmegen Sulfide Ammonia to 5.0% by weight of a compound of formula I and from Content Content Content 5 to 20% by weight of said deodorizing agent for am- 5 (ppm) (ppm) (ppm) monia and amines. Further, in order to sterilize bad b f r addition 9 35 smell-giving microorganisms and to prevent bad smells z gg S 0 I s from occurring anew, it is possible to incorporate in the 4 ft i deodorizing agent of this invention a known fungicide l0 z t i 0 0 0 such, for instance, as benzalkomum chloride, alkyl pyradd-mun 0 0 0 idinium bromide, chloracetamide, phenol and cresol. The amount of said fungicide is from 0.1 to 3.0% by weight Example 4 I The smell-sweetening and deodorizing agent is gener- An aqueous so'lullon' comammg 1% of ally used in the form of an aqueous solution or a watercarbon/methyl male'mlfle and 2% of glyoxa] was tested alcohol solution, the alcohols being alkanolshaving 1 if the g m gma i P The excellent to 3 carbon atoms. In case the dissolution of the active acts 8 own m a B were obtamed' ingredient is insufficient, it may be used in the form of Table 4 an emulsion without any disadvantage. In somecases it may be used in a powdery or granular form. The agent Mcercapwn y gs Sulfide Acmmonifl ean be applied, in the above-mentioned forms, to odor- 32:? 32:? 32:? iferous materials and/or odoriferous ob ects and surfaces to remove the odor caused by hydrogen sulfide, 2153:3332? 20 mercaptans and like materials. addition l3 0 o This invention will now be described in greater detail g 0 0 0 by reference to the following illustrative Examples. 6 hours after Example 1 addition 0 0 o A mixture of fish meat, peptone, glucose and water wai gutrefied at 4: 1C folr about 2f0riliouas,land ll mlgf Example 5 a 0 water'a W2 0 y ma e A mixture of fish meat, peptone, glucose and water (water/alcohol weight ratio -9/l was added dropwise was putrefied at for about 20 hours and 1 ml of to 30 g of the Putrefied mmure- The a 1% water-alcohol solution of 3-methyl maleimide captan and y g Sulfide W determmed l (water/alcohol weight ratio 8/2) was added dropwise vals. The excellent removal CffeCtS as ShQWI'l m Table to g of the putrefied mixture The amounts of mer- 2 were obtained. captan and hydrogen sulfide were determined at inter- Table 2 40 vals. The excellent results as shown in Table 5 were obtained.

, Contents of Mercuptan and Hydrogen Table 5 Sulfide Mercuptan (ppm) Hydrtiiirzniulfide M83355?" Hy l'ggil'tleilillfidc (pp (p before dddilitm 300 40 bcfore addition 7 5 l ddilion )0 7 l hour after addition 70 10 2 hours after addition 45 U 2 hours after addition 40 0 3 hours after addition it) 0 3 hours after addition 12 0 4 hours after addition 3 0 4 hours after addition 2 0 Example 2 Example 6 In the same manner as in Example 1, tests were con- In the szjlme manner as m Example}, tests f'? ducted with the use of 1% water-alcohol solutions conducted water'alcqhol Soluuons q f taining maleimide, N-methyl maleimide, N-nonyl Ethyl F fg 3 z g g maleimide, N-phenyl maleimide and 2-hydroxyethyl romoma *"T" P P oroma N- methyl-3,4-d1chloromale1m1de and N-phenylmethylmaleimide, respectively (water/alcohol weight ratio Similar results to those Obtained in Exam 1e 1 6 chloromaleimtde, respectively (water/alcohol weight p 0 ratio 7/3 Similar results to those obtained in Examwere obtained E l 3 pie 1 were obtained.

Xamp e Example 7 In the f manner as m Exampledt a test W 3 In the same manner as in Example 1, a test was efducted using 1 ml of an aqueous solution containing 1% f t d using 1 ml of an aqueous SoIution containing 1% of 3-methyl maleimide, 2% of glyoxal and 0.4% of benzalkonium chloride. The results obtained were excellent as shown in Table 6.

Table 6 Mercaptan Hydrogen Sulfide Ammonia Content Content Content (pp (pp (pp before addition 210 40 120 l hour after addition 55 8 50 2 hours after addition 30 l 3 hours after addition 7 (l 7 4 hours after addition 1 0 (J Example 8 2 ml of an aqueous solution containing 0.5% of N- hydroxymethyl maleimide, 3% of malic acid, 3% of phosphoric acid and 1.5% of glyoxal was added to a bad'smelling system comprising 100 g of putrefied excrements put in a 1 litre bottle and the amounts of mercaptan, hydrogen sulfide and ammonia in the head space of the bottle were determined at intervals. The excellent deodorizing effects as shown in Table 7 were obtained. Further, a remarkable deodorizing effect was also recognized by the judgement through the olfactory sensation.

The values in parenthesis show corresponding data in case of non-addition of deodorizing agent.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

l. A method for deodorizing and sweetening the smell of odoriferous materials and objects characterized by having mercaptans and hydrogen sulfide as a bad-smelling component, which comprises applying to said material or object an effective deodorizing amount of a compound of the formula:

wherein R, is selected from the group consisting of hydrogen, alkyl, having one to 12 carbon atoms, hydroxymethyl, 2-hydroxyethyl, carboxymethyl, Z-aminoethyl, phenyl, alkyl substituted phenyl wherein the alkyl has one to three carbon atoms,

anilino and phenylhydrazo;

R and R each is selected from the group consisting of hydrogen, halogen, alkyl having one to 12 carbon atoms, hydroxymethyl, 2-hydroxyethyl, carboxymethyl, Z-aminoethyl, phenyl, alkyl substituted phenyl wherein the alkyl has one to three carbon atoms, anilino and phenylhydrazo;

in an amount sufficient to substantially reduce the mercaptan and hydrogen sulfide content of the odoriferous material or object.

2. The method according to claim 1, wherein said applying is accomplished by dissolving or suspending said deodorizing compound in water or a mixture of water and an alkanol having one to three carbon atoms, and applying the dissolved or suspended compound to the odoriferous material or object.

* l l l 

1. A METHOD FOR DEODORIZING AND SWEETENING THE SMELL OF ODORIFERROUS MATERIALS AND OBJECTS CHARACTERIZED BY HAVING MERCAPTANS AND HYDROGEN SULFIDE AS A BAD-SMELLING COMPONENT, WHICH COMPRISES APPLYING TO SAID MATERIAL OR OBJECT AN EFFECTIVE DEODORIZING AMOUNT OF A COMPOUND OF THE FORMULA:
 2. The method according to claim 1, wherein said applying is accomplished by dissolving or suspending said deodorizing compound in water or a mixture of water and an alkanol having one to three carbon atoms, and applying the dissolved or suspended compound to the odoriferous material or object. 